CN103044365B - Production method of tetrahydrofuran - Google Patents
Production method of tetrahydrofuran Download PDFInfo
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- CN103044365B CN103044365B CN201110313844.8A CN201110313844A CN103044365B CN 103044365 B CN103044365 B CN 103044365B CN 201110313844 A CN201110313844 A CN 201110313844A CN 103044365 B CN103044365 B CN 103044365B
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Abstract
The invention discloses a production method of tetrahydrofuran. The tetrahydrofuran is produced from coarse 1,4-butanediol containing 2-(4'-hydroxybutoxyl) tetrahydrofuran through continuously cyclodehydrating under the action of a palladium-supported sulfonated ion exchange resin catalyst in the presence of hydrogen. The palladium-supported sulfonated ion exchange resin catalyst generally contains 0.02-1.50% of palladium, the cyclodehydration is generally carried out under the reaction conditions that the hydrogen and the raw material (100% of 1,4-butanediol) are in the molar ratio of 1-100, the reaction temperature is 50-170 DEG C, the reaction pressure is 0.02-2.0MPa, and the liquid hour (volume) space velocity of 1,4-butanediol is 0.5-5.0h<-1>. According to the method, 1,4-butanediol containing 2-(4'-hydroxybutoxyl) tetrahydrofuran is used as a raw material, the high-selectivity tetrahydrofuran is produced continuously and stably in a long period under the condition of low temperature, and the method is suitable for industrial application.
Description
Technical field
The present invention relates to a kind of preparation method of tetrahydrofuran (THF), relating in particular to a kind of take BDO as the method that tetrahydrofuran (THF) is prepared in raw material dehydration cyclisation.
Background technology
Tetrahydrofuran (THF) (THF) is the low poison solvent of a kind of high polarity, lower boiling, excellent property, be widely used as the solvent of topcoating, protective system and film coating, its topmost purposes produces polytetramethylene ether diol (PTMEG), polyurethane elastomer and polyurethane artificial leather etc., is also used as the solvent of esterification and polyreaction and some medicine intermediates as the raw material etc. of hormone drug.
At present, the production method of tetrahydrofuran (THF) has: hydrogenation of furfural method, cis-butenedioic anhydride directed hydrogenation and BDO cyclodehydration method.Wherein furfural method is due to complex process, and raw material consumption is high, is seriously pollutedly eliminated gradually.Cis-butenedioic anhydride directed hydrogenation using cis-butenedioic anhydride directly as raw material, first it is soluble in water, be prepared into the cis-butenedioic anhydride aqueous solution of 35%, because this solution has very strong corrodibility, expensive anticorrosion material must be adopted, catalyzer adopts Pd-Re/C catalyzer, and under the high pressure of 17 ~ 35MPa, carry out hydrogenation, these all make the fixed investment of this technique and process cost significantly rise.
BDO cyclodehydration method is the main method of producing tetrahydrofuran (THF) at present.The method being prepared tetrahydrofuran (THF) by BDO is for a long time known, and known method is the method by the dehydration of interpolation phosphoric acid, sulfuric acid or acidic ion exchange resin, BDO being converted into tetrahydrofuran (THF).According in partial continuous process, be then mixed with the BDO of acid simultaneously in heating, and continue to add BDO, in an amount equivalent to the amount of the tetrahydrofuran (THF)/water removed.As everyone knows, if adopt corrosive sulfuric acid, then need special anticorrosion equipment, the investment of equipment is increased, and the spent acid of generation also pollutes the environment.Also can produce coke-like material in reaction process in addition, the complicacy of reaction process is increased greatly.
SU 1426973 discloses a kind of with γ-Al
2o
3or chloride γ-Al
2o
3for the technique of catalyst preparing tetrahydrofuran (THF), 320 DEG C, react under condition of normal pressure.When BDO liquid hourly space velocity is 7.0 h
-1time, the transformation efficiency of BDO is 100%, and the selectivity of tetrahydrofuran (THF) is 100%.And when the liquid hourly space velocity of BDO is increased to 7.5 h
-1time, the transformation efficiency of BDO drops to 97.4%, and the selectivity of tetrahydrofuran (THF) drops to 93.6%.
No. 51-76263rd, JP discloses a kind of with unformed SiO
2-Al
2o
3as the method for catalyst preparing tetrahydrofuran (THF), fixed bed is adopted to carry out gas-solid phase reaction, at 250 DEG C, SiO
2content is the SiO of 87%
2-Al
2under O catalyst action, tetrahydrofuran (THF) yield is 97%, and the processing power of BDO is 1g/g
cat.h.
CN 1283620 discloses a kind of 1, the method of tetrahydrofuran (THF) is prepared in the cyclisation of 4-Butanediol, at 170 ~ 250 DEG C, make 1,4-butyleneglycol contacts with HZSM-5 molecular sieve catalyst and reacts, every gram of catalyzer is per hour can process BDO 100 ~ 1300 grams, tetrahydrofuran (THF) selectivity 99.5%.
CN 1306961 discloses a kind of 1, the method of tetrahydrofuran (THF) is prepared in the cyclisation of 4-Butanediol, at 120 ~ 250 DEG C, make 1,4-butyleneglycol contacts with Y or beta-zeolite catalyst and reacts, every gram of catalyzer is per hour can process BDO 100 ~ 1400 grams, tetrahydrofuran (THF) selectivity 99.8%.
CN 1504466 and CN 1271730 individually discloses with η-Al
2o
3and X-Al
2o
3for catalyzer carries out BDO preparing tetrahydrofuran by dehydrating and cyclization, at the temperature more than 200 DEG C, achieve very well results.
In the production method of above-mentioned disclosed tetrahydrofuran (THF), although the transformation efficiency of report and selectivity very high, be difficult to avoid BDO intermolecular polymerization to form dipolymer or superpolymer under above-mentioned higher temperature of reaction; Simultaneously expertise also tells that we adopt aluminum oxide or zeolite molecular sieve is the framework dealumination that catalyzer is also difficult to avoid catalyzer at high water vapor environment, these factors affect industrial application of this type of catalyzer.
For the problems referred to above, CN1686610 discloses a kind of method preparing tetrahydrofuran (THF), with load type silicotungstic acid (content 5 ~ 25%) as catalyzer, by catalyzer and 1, the mass ratio of 4-butyleneglycol is that 1:300 adds in reaction system, adopt catalytic distillation device cyclisation Dehydration for tetrahydrofuran (THF), this catalyzer has good catalytic activity.
CN 1272495 discloses a kind of tetrahydrofuran (THF) production method, at 130 ~ 250 DEG C of temperature, goes out to contact react catalyzer and the Isosorbide-5-Nitrae-Ding containing heteropolyacid, and every gram of heteropolyacid is per hour processes BDO 1000 ~ 2000 grams.
It take strong acid ion exchange resin as the method that catalyzer carries out BDO preparing tetrahydrofuran by dehydrating and cyclization that CN 101298444 discloses a kind of, and temperature of reaction controls, at 50 ~ 150 DEG C, to reduce running cost.
But, in above-mentioned disclosed patent, all do not mention the impact that the character of BDO raw material is reacted cyclodehydration.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of 1, the method of tetrahydrofuran (THF) is produced in the cyclisation of 4-Butanediol, the method is with containing thick 1 of 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF), 4-butyleneglycol is raw material, and long-cycle production continual and steady under the condition of low temperature goes out the tetrahydrofuran (THF) of highly selective.
A kind of production method of tetrahydrofuran (THF), with containing thick 1 of 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF), 4-butyleneglycol is raw material, and the sulfonate ion exchange resin catalyzer continuing through a kind of year palladium under hydro condition carries out cyclodehydration and produces tetrahydrofuran (THF).
The thick BDO containing 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) described in the inventive method is from taking cis-butenedioic anhydride as the BDO product that raw material obtains after esterification, hydrogenation, separating-purifying.In this BDO product, content meter contains 2-(4-hydroxybutoxy) tetrahydrofuran (THF) of 0.05% ~ 1.00% by weight.
The sulfonate ion exchange resin catalyzer carrying palladium described in the inventive method can adopt commercially available commercial grade catalyzer also can make by oneself according to prior art.In this catalyzer, the general content of the weight of palladium is 0.02% ~ 1.50%, preferably 0.05% ~ 1.00%.Described sulfonate ion exchange resin is strong acid type styrene ion exchange resin, and resin butt exchange capacity is 4.00 ~ 4.20 mol/g, wet density 0.69 ~ 0.75g/cm
3, percentage of water loss 58 ~ 62%, mean pore size 5.0 × 10
-9~ 30.0 × 10
-9m, preferably 12.0 × 10
-9~ 18.0 × 10
-9m, specific surface area 10 ~ 100m
2/ g, preferably 20 ~ 50m
2/ g.
Cyclodehydration reaction conditions described in the inventive method is generally hydrogen and raw material (by 100%1,4-butyleneglycol meter) mol ratio is 1 ~ 100, temperature of reaction is 50 ~ 170 DEG C, answers pressure to be 0.02 ~ 2.0MPa, volume space velocity 0.5 ~ 5.0 h during BDO liquid
-1.
Cyclodehydration reaction conditions described in the inventive method is preferably hydrogen and raw material (by 100%1,4-butyleneglycol meter) mol ratio is 3 ~ 20, temperature of reaction is 80 ~ 120 DEG C, answers pressure to be 0.1 ~ 1.0MPa, during BDO liquid, volume space velocity is 1.0 ~ 3.0 h
-1.
Cyclodehydration reaction described in the inventive method adopts fixed bed mode to carry out, and reaction can be shell and tube-type reactor, adiabatic operation.
1, in 4-butyleneglycol production process, especially obtaining producing in the process of BDO through esterification, hydrogenation with maleic anhydride of enforcement at present, the byproduct of generation---cyclic acetal class material and 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) are difficult to avoid.Although, 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) growing amount is little, but due to 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) and product 1,4-butyleneglycol forms minimum azeotrope, its constant boiling point and 1,4-butyleneglycol is very close, is difficult to merely be separated this byproduct by conventional rectification.And 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) in acid condition, can be transformed into 2,3 dihydro furan and BDO, 2,3 dihydro furan is very easy to polymerization under acid effect; Under acid and water existence condition, the hydrolysis of 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) forms BDO and acetaldol (or 2-hydroxyl tetrahydrofuran), and acetaldol can be polymerized equally.Above-mentioned polymkeric substance can be gathered in the surface of catalyzer, affects the activity stability of catalyzer, and the transformation efficiency of BDO can be made during long-term operation obviously to decline.
Present approach provides one by the BDO containing 2-(4-hydroxybutoxy) tetrahydrofuran (THF) in the method for facing the sulfonate ion exchange resin catalyzer cyclodehydration production tetrahydrofuran (THF) continuing through a kind of year palladium under hydrogen state.In this process, under the acting in conjunction of hydrogen and palladium, can not only suppress the polyreaction of 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF), and the polymkeric substance generation hydrogenation reaction that 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) can be made to generate in acid condition generates tetrahydrofuran (THF).Thus reduce its gathering at catalyst surface, improve the stability of catalyzer and the transformation efficiency of BDO, under the same terms, the transformation efficiency of BDO can improve more than 10%.
Except above-mentioned carried advantage, compared with prior art, the inventive method also has following beneficial effect:
(1) in the tetrahydrofuran (THF) product that prepared by the inventive method, it is few that 2,3 dihydro furan, DHF, 2,3 dihydro furan etc. are not easy to the product assay that tetrahydrofuran (THF) is separated, and is conducive to the separation of tetrahydrofuran (THF) and improves the purity of tetrahydrofuran (THF);
(2) in the inventive method, dehydration reaction process is carried out facing under hydrogen state, the existence of hydrogen is carried out except hydrogenation except what discussed before having to intermediate product, can also ensure that the tetrahydrofuran (THF) that generates in reaction process and water exist with gas phase, favourable chemical equilibrium of breaking reaction, suppress side reaction to occur simultaneously, extending catalyst work-ing life, improve the transformation efficiency of BDO;
(3) owing to have employed strongly acidic ion-exchange resin catalyst, reaction can be carried out at relatively low temperatures and pressures, catalyzer non-corrosiveness, reaction process does not need specific installation, reduces investment and running cost.
Embodiment
The functions and effects of the inventive method are illustrated below in conjunction with embodiment.Percentage composition involved in embodiment and comparative example is mass percentage.
Embodiment 1
Fixed bed isothermal reactor is adopted to consist of 1, palladium resin catalyst is continued through after the raw material of 4-butyleneglycol 99.52%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.48% mixes with hydrogen, adopt the palladium content 0.05% of catalyzer, resin adopts the commercially available trade mark to be D005 type large hole cation exchanger resin.Control temperature of reaction 100 DEG C, reaction pressure 0.6MPa, hydrogen alcohol mol ratio 10, BDO liquid hourly space velocity 1.5h
-1, reaction product collects liquid product after deep cooling, forms with gas chromatographic analysis.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Embodiment 2
Fixed bed isothermal reactor is adopted to consist of 1, palladium resin is continued through after the raw material of 4-butyleneglycol 99.52%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.48% mixes with hydrogen, adopt the palladium content 0.05% of catalyzer, resin adopts the commercially available trade mark to be D005 type large hole cation exchanger resin.Control temperature of reaction 100 DEG C, reaction pressure 0.2MPa, hydrogen alcohol mol ratio 6, BDO liquid hourly space velocity 1.0h
-1, reaction product collects liquid product after deep cooling, forms with gas chromatographic analysis.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Embodiment 3
Fixed bed isothermal reactor is adopted to consist of 1, palladium resin catalyst is continued through after the raw material of 4-butyleneglycol 99.22%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.78% mixes with hydrogen, adopt the palladium content 0.07% of catalyzer, resin adopts the commercially available trade mark to be D72 type large hole cation exchanger resin.Control temperature of reaction 100 DEG C, reaction pressure 0.6MPa, hydrogen alcohol mol ratio 10, BDO liquid hourly space velocity 1.5h
-1, reaction product collects liquid product after deep cooling, forms with gas chromatographic analysis.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Embodiment 4
Fixed bed isothermal reactor is adopted to consist of 1, palladium resin catalyst is continued through after the raw material of 4-butyleneglycol 99.22%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.78% mixes with hydrogen, adopt the palladium content 0.07% of catalyzer, resin adopts the commercially available trade mark to be D72 type large hole cation exchanger resin.Control temperature of reaction 80 DEG C, reaction pressure 0.1MPa, hydrogen alcohol mol ratio 20, BDO liquid hourly space velocity 1.0 h
-1, reaction product collects liquid product after deep cooling, forms with gas chromatographic analysis.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Embodiment 5
Fixed bed isothermal reactor is adopted to consist of 1, palladium resin catalyst is continued through after the raw material of 4-butyleneglycol 99.52%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.48% mixes with hydrogen, adopt the palladium content 0.05% of catalyzer, resin adopts the commercially available trade mark to be D005 type large hole cation exchanger resin.Control temperature of reaction 120 DEG C, reaction pressure 1.0MPa, hydrogen alcohol mol ratio 20, BDO liquid hourly space velocity 1.5h
-1, reaction product collects liquid product after deep cooling, forms with gas chromatographic analysis.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Embodiment 6
Fixed bed isothermal reactor is adopted to consist of 1, palladium resin catalyst is continued through after the raw material of 4-butyleneglycol 99.52%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.48% mixes with hydrogen, adopt the palladium content 0.05% of catalyzer, resin adopts the commercially available trade mark to be D005 type large hole cation exchanger resin.Control temperature of reaction 100 DEG C, reaction pressure 0.3MPa, hydrogen alcohol mol ratio 10, BDO liquid hourly space velocity 2.5h
-1, reaction product collects liquid product after deep cooling, forms with gas chromatographic analysis.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Embodiment 7
Fixed bed isothermal reactor is adopted to consist of 1, palladium resin catalyst is continued through after the raw material of 4-butyleneglycol 99.12%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.46%, gamma-butyrolactone 0.42% mixes with hydrogen, adopt the palladium content 0.09% of catalyzer, resin adopts the commercially available trade mark to be D005 type large hole cation exchanger resin.Control temperature of reaction 100 DEG C, reaction pressure 0.3MPa, hydrogen alcohol mol ratio 5, BDO liquid hourly space velocity 2.5h
-1, reaction product collects liquid product after deep cooling, forms with gas chromatographic analysis.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Comparative example 1
Palladium metal is described in catalyzer and faces the effect of hydrogen for cyclodehydration.Adopt the catalyzer not having the same resin of supported palladium to react as cyclodehydration.Fixed bed isothermal reactor is adopted to consist of 1, the raw material of 4-butyleneglycol 99.52%, 2-(4-hydroxybutoxy) tetrahydrofuran (THF) 0.48% continues through resin catalyst, adopts the commercially available trade mark to be that D005 type large hole cation exchanger resin is as catalysts.Control temperature of reaction 100 DEG C, reaction pressure 0.6MPa, BDO liquid hourly space velocity 1.5h
-1, reaction product collects liquid product after deep cooling, and with gas chromatographic analysis composition, reaction conditions and reaction result are in table 1.Run 500 hours continuously with this understanding, reaction conditions and reaction result are in table 1.
Table 1
| Reaction conditions | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 |
| Temperature of reaction, DEG C | 100 | 100 | 100 | 80 | 120 | 100 | 100 | 100 |
| Reaction pressure, MPa | 0.6 | 0.2 | 0.6 | 0.1 | 1.0 | 0.3 | 0.3 | 0.6 |
| Air speed, h -1 | 1.5 | 1.0 | 1.5 | 1.0 | 1.5 | 2.5 | 2.5 | 1.5 |
| Hydrogen alcohol mol ratio | 10 | 6 | 12 | 20 | 20 | 10 | 5 | - |
| Reaction product gas chromatographic analysis result (%) | ||||||||
| BDO | 12.86 | 11.85 | 11.94 | 15.36 | 14.42 | 16.92 | 18.91 | 20.97 |
| 2-(4-hydroxybutoxy) tetrahydrofuran (THF) | 0.27 | 0.25 | 0.35 | 0.37 | 0.21 | 0.28 | 0.23 | 0.14 |
| Tetrahydrofuran (THF) | 69.61 | 69.85 | 69.57 | 67.87 | 68.36 | 66.81 | 65.13 | 63.55 |
| 2,3 dihydro furan | 0.00 | 0.01 | 0.00 | 0.02 | 0.00 | 0.00 | 0.01 | 0.13 |
| DHF | - | 0.00 | - | 0.00 | - | - | - | 0.01 |
| 2-hydroxyl tetrahydrofuran | 0.01 | 0.01 | 0.02 | 0.02 | 0.00 | 0.01 | 0.01 | 0.07 |
| Water | 17.25 | 18.03 | 18.12 | 16.36 | 17.01 | 15.98 | 15.28 | 15.13 |
| Gamma-butyrolactone | － | - | - | - | - | - | 0.43 | － |
By known above, under the condition of long-term operation, the inventive method can significantly improve the stability of working unit.
Claims (6)
1. the production method of a tetrahydrofuran (THF), it is characterized in that: the method is with containing thick 1 of 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF), 4-butyleneglycol is raw material, under hydro condition, continue through the sulfonate ion exchange resin catalyzer carrying palladium carry out cyclodehydration production tetrahydrofuran (THF), the sulfonate ion exchange resin catalyzer carrying palladium adopts commercially available commercial grade catalyzer, the weight content carrying palladium in the sulfonate ion exchange resin catalyzer of palladium is 0.05% ~ 1.00%, carrying sulfonate ion exchange resin in the sulfonate ion exchange resin catalyzer of palladium is strong acid type styrene ion exchange resin, resin butt exchange capacity is 4.00 ~ 4.20 mol/g, wet density 0.69 ~ 0.75g/cm
3, percentage of water loss 58 ~ 62%, mean pore size 5.0 × 10
-9~ 30.0 × 10
-9m, specific surface area 10 ~ 100m
2/ g.
2. method according to claim 1, is characterized in that: the described thick BDO containing 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) is from taking cis-butenedioic anhydride as the BDO product that raw material obtains after esterification, hydrogenation, separating-purifying.
3. method according to claim 1 and 2, is characterized in that: in described BDO, content meter contains 2-(4 '-hydroxybutoxy) tetrahydrofuran (THF) of 0.05% ~ 1.00% by weight.
4. method according to claim 1, is characterized in that: described carries sulfonate ion exchange resin mean pore size 12.0 × 10 in the sulfonate ion exchange resin catalyzer of palladium
-9~ 18.0 × 10
-9m, specific surface area 20 ~ 50m
2/ g.
5. method according to claim 1, it is characterized in that: described cyclodehydration reaction conditions is that hydrogen and raw material are by 100%1,4-butyleneglycol meter mol ratio is 1 ~ 100, temperature of reaction is 50 ~ 170 DEG C, reaction pressure is 0.02 ~ 2.0MPa, volume space velocity 0.5 ~ 5.0 h during BDO liquid
-1.
6. method according to claim 5, it is characterized in that: described cyclodehydration reaction conditions is preferably hydrogen and raw material by 100%1,4-butyleneglycol meter mol ratio is 3 ~ 20, temperature of reaction is 80 ~ 120 DEG C, pressure is answered to be 0.1 ~ 1.0MPa, during BDO liquid, volume space velocity is 1.0 ~ 3.0 h
-1.
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| CN111170968B (en) * | 2020-01-13 | 2020-10-27 | 北京笃敬科技有限公司 | System and method for preparing tetrahydrofuran |
| CN114874074B (en) * | 2022-05-27 | 2023-06-13 | 辽宁石油化工大学 | Separation and purification process and system for 1, 4-butanediol |
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| CN101163656A (en) * | 2004-07-01 | 2008-04-16 | 英尼奥斯美国有限责任公司 | Catalysts for maleic acid hydrogenation to 1,4-butanediol |
| CN101298444A (en) * | 2008-05-30 | 2008-11-05 | 中化国际（苏州）新材料研发有限公司 | Method for preparing tetrahydrofuran by dehydration and cyclization of 1,4-butanediol |
| CN101356166A (en) * | 2006-01-10 | 2009-01-28 | Sk株式会社 | Method for preparing 3-hydroxytetrahydrofuran by cyclodehydration |
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| JP3168548B2 (en) * | 1992-11-19 | 2001-05-21 | 東ソー株式会社 | Method for producing tetrahydrofuran |
| JPH06179667A (en) * | 1992-12-14 | 1994-06-28 | Tosoh Corp | Production of tetrahydrofuran |
| JP2001011000A (en) * | 1999-06-28 | 2001-01-16 | Mitsubishi Chemicals Corp | Method for producing 1,4-butanediol and/or tetrahydrofuran |
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| CN101356166A (en) * | 2006-01-10 | 2009-01-28 | Sk株式会社 | Method for preparing 3-hydroxytetrahydrofuran by cyclodehydration |
| CN101298444A (en) * | 2008-05-30 | 2008-11-05 | 中化国际（苏州）新材料研发有限公司 | Method for preparing tetrahydrofuran by dehydration and cyclization of 1,4-butanediol |
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